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Title: 1,2-Addition of Formic or Oxalic Acid to N{CH 2CH 2(PiPr 2)} 2 -Supported Mn(I) Dicarbonyl Complexes and the Manganese-Mediated Decomposition of Formic Acid

Abstract

(PN HP)Mn(CO) 2 (I) carboxylate complexes (PN HP = HN{CH 2CH 2(PiPr 2)} 2) were prepared in this study via 1,2-addition of either formic or oxalic acid to (PNP)Mn(CO) 2 (PNP = the deprotonated, amide form of the ligand –N{CH 2CH 2(PiPr 2)} 2). The structural and spectral properties of these complexes were compared. The manganese formate complex was found to be dimeric in the solid state and monomeric in solution. Half an equivalent of oxalic acid was employed to form the bridging oxalate dimanganese complex. The catalytic competencies of the carboxylate complexes were assessed, and the formate complex was found to decompose formic acid catalytically. Both dehydrogenation and dehydration pathways were active as assessed by the presence of H 2, CO 2, and H 2O. Lastly, the addition of LiBF 4 exhibited a strong inhibitory effect on the catalysis.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1483496
Report Number(s):
LA-UR-16-22530
Journal ID: ISSN 0276-7333
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 35; Journal Issue: 12; Journal ID: ISSN 0276-7333
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Tondreau, Aaron M., and Boncella, James M. 1,2-Addition of Formic or Oxalic Acid to –N{CH2CH2(PiPr2)}2 -Supported Mn(I) Dicarbonyl Complexes and the Manganese-Mediated Decomposition of Formic Acid. United States: N. p., 2016. Web. doi:10.1021/acs.organomet.6b00274.
Tondreau, Aaron M., & Boncella, James M. 1,2-Addition of Formic or Oxalic Acid to –N{CH2CH2(PiPr2)}2 -Supported Mn(I) Dicarbonyl Complexes and the Manganese-Mediated Decomposition of Formic Acid. United States. doi:10.1021/acs.organomet.6b00274.
Tondreau, Aaron M., and Boncella, James M. Tue . "1,2-Addition of Formic or Oxalic Acid to –N{CH2CH2(PiPr2)}2 -Supported Mn(I) Dicarbonyl Complexes and the Manganese-Mediated Decomposition of Formic Acid". United States. doi:10.1021/acs.organomet.6b00274. https://www.osti.gov/servlets/purl/1483496.
@article{osti_1483496,
title = {1,2-Addition of Formic or Oxalic Acid to –N{CH2CH2(PiPr2)}2 -Supported Mn(I) Dicarbonyl Complexes and the Manganese-Mediated Decomposition of Formic Acid},
author = {Tondreau, Aaron M. and Boncella, James M.},
abstractNote = {(PNHP)Mn(CO)2 (I) carboxylate complexes (PNHP = HN{CH2CH2(PiPr2)}2) were prepared in this study via 1,2-addition of either formic or oxalic acid to (PNP)Mn(CO)2 (PNP = the deprotonated, amide form of the ligand –N{CH2CH2(PiPr2)}2). The structural and spectral properties of these complexes were compared. The manganese formate complex was found to be dimeric in the solid state and monomeric in solution. Half an equivalent of oxalic acid was employed to form the bridging oxalate dimanganese complex. The catalytic competencies of the carboxylate complexes were assessed, and the formate complex was found to decompose formic acid catalytically. Both dehydrogenation and dehydration pathways were active as assessed by the presence of H2, CO2, and H2O. Lastly, the addition of LiBF4 exhibited a strong inhibitory effect on the catalysis.},
doi = {10.1021/acs.organomet.6b00274},
journal = {Organometallics},
issn = {0276-7333},
number = 12,
volume = 35,
place = {United States},
year = {2016},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
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Citation Metrics:
Cited by: 38 works
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Figures / Tables:

Figure 1 Figure 1: Comparison of isoelectronic metal complexes of Fe(II) and Mn(I).

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Works referencing / citing this record:

Hydrogenation of Carbonyl Derivatives Catalysed by Manganese Complexes Bearing Bidentate Pyridinyl-Phosphine Ligands
journal, December 2017

  • Wei, Duo; Bruneau-Voisine, Antoine; Chauvin, Téo
  • Advanced Synthesis & Catalysis, Vol. 360, Issue 4
  • DOI: 10.1002/adsc.201701115

A Highly Active Manganese Catalyst for Enantioselective Ketone and Ester Hydrogenation
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  • Widegren, Magnus B.; Harkness, Gavin J.; Slawin, Alexandra M. Z.
  • Angewandte Chemie International Edition, Vol. 56, Issue 21
  • DOI: 10.1002/anie.201702406

Manganese-Catalyzed Sustainable Synthesis of Pyrroles from Alcohols and Amino Alcohols
journal, May 2017

  • Kallmeier, Fabian; Dudziec, Beata; Irrgang, Torsten
  • Angewandte Chemie International Edition, Vol. 56, Issue 25
  • DOI: 10.1002/anie.201702543

Manganese(I)-Catalyzed Enantioselective Hydrogenation of Ketones Using a Defined Chiral PNP Pincer Ligand
journal, August 2017

  • Garbe, Marcel; Junge, Kathrin; Walker, Svenja
  • Angewandte Chemie International Edition, Vol. 56, Issue 37
  • DOI: 10.1002/anie.201705471

Manganese-Catalyzed Direct Olefination of Methyl-Substituted Heteroarenes with Primary Alcohols
journal, June 2018

  • Barman, Milan K.; Waiba, Satyadeep; Maji, Biplab
  • Angewandte Chemie International Edition, Vol. 57, Issue 29
  • DOI: 10.1002/anie.201804729

Oxidative Transformations of Biosourced Alcohols Catalyzed by Earth-Abundant Transition Metals
journal, June 2017


Benzylene-linked [PNP] scaffolds and their cyclometalated zirconium and hafnium complexes
journal, January 2017

  • Sietzen, Malte; Batke, Sonja; Antoni, Patrick W.
  • Dalton Transactions, Vol. 46, Issue 18
  • DOI: 10.1039/c7dt00413c

Carbon dioxide hydrogenation catalysed by well-defined Mn( i ) PNP pincer hydride complexes
journal, January 2017

  • Bertini, Federica; Glatz, Mathias; Gorgas, Nikolaus
  • Chemical Science, Vol. 8, Issue 7
  • DOI: 10.1039/c7sc00209b

Hydrogenation of Carbonyl Derivatives Catalysed by Manganese Complexes Bearing Bidentate Pyridinyl-Phosphine Ligands
journal, December 2017

  • Wei, Duo; Bruneau-Voisine, Antoine; Chauvin, Téo
  • Advanced Synthesis & Catalysis, Vol. 360, Issue 4
  • DOI: 10.1002/adsc.201701115

Manganese-Catalyzed Direct Olefination of Methyl-Substituted Heteroarenes with Primary Alcohols
journal, June 2018

  • Barman, Milan K.; Waiba, Satyadeep; Maji, Biplab
  • Angewandte Chemie, Vol. 130, Issue 29
  • DOI: 10.1002/ange.201804729

A Highly Active Manganese Catalyst for Enantioselective Ketone and Ester Hydrogenation
journal, April 2017

  • Widegren, Magnus B.; Harkness, Gavin J.; Slawin, Alexandra M. Z.
  • Angewandte Chemie International Edition, Vol. 56, Issue 21
  • DOI: 10.1002/anie.201702406

Manganese-Catalyzed Sustainable Synthesis of Pyrroles from Alcohols and Amino Alcohols
journal, May 2017

  • Kallmeier, Fabian; Dudziec, Beata; Irrgang, Torsten
  • Angewandte Chemie International Edition, Vol. 56, Issue 25
  • DOI: 10.1002/anie.201702543

Manganese(I)-Catalyzed Enantioselective Hydrogenation of Ketones Using a Defined Chiral PNP Pincer Ligand
journal, August 2017

  • Garbe, Marcel; Junge, Kathrin; Walker, Svenja
  • Angewandte Chemie International Edition, Vol. 56, Issue 37
  • DOI: 10.1002/anie.201705471

Oxidative Transformations of Biosourced Alcohols Catalyzed by Earth-Abundant Transition Metals
journal, June 2017


Benzylene-linked [PNP] scaffolds and their cyclometalated zirconium and hafnium complexes
journal, January 2017

  • Sietzen, Malte; Batke, Sonja; Antoni, Patrick W.
  • Dalton Transactions, Vol. 46, Issue 18
  • DOI: 10.1039/c7dt00413c

Carbon dioxide hydrogenation catalysed by well-defined Mn( i ) PNP pincer hydride complexes
journal, January 2017

  • Bertini, Federica; Glatz, Mathias; Gorgas, Nikolaus
  • Chemical Science, Vol. 8, Issue 7
  • DOI: 10.1039/c7sc00209b

Manganese(I)-Catalyzed Enantioselective Hydrogenation of Ketones Using a Defined Chiral PNP Pincer Ligand
journal, August 2017

  • Garbe, Marcel; Junge, Kathrin; Walker, Svenja
  • Angewandte Chemie, Vol. 129, Issue 37
  • DOI: 10.1002/ange.201705471

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